EP3052075A1

EP3052075A1 - Hair treatment agents containing oligopeptides and hyaluronic acid esters

Info

Publication number: EP3052075A1
Application number: EP14799663.1A
Authority: EP
Inventors: Volker Scheunemann; Erik Schulze Zur Wiesche
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2013-10-02
Filing date: 2014-09-24
Publication date: 2016-08-10
Also published as: WO2015048965A1; DE102013220061A1; US20160199281A1; CN105592842A

Abstract

The invention relates to hair treatment agents containing, with respect to the weight thereof, 0.0001 - 10 wt.-% of at least one oligopeptide which has at least one amino acid sequence Glu-glu-Glu (formula (I)), the amino groups can be free or protonated and the carboxyl groups can be free or deprotonated, and 0.0001 - 10 wt.-% of at least one hyaluronic acid ester with lipoic acid, formic acid or mixtures thereof. In the agents, the hyaluronic acid ester and specific oligopeptides reinforce the positive effect on the hair and hair follicles.

Description

HAIR TREATING AGENTS CONTAINING OLIGOPEPTIDES AND ESTERS OF HYALURONIC ACID

The invention relates to hair treatment compositions, in particular so-called conditioners, with a combination of active ingredients for gentle and effective hair care.

Not least due to the heavy use of hair, for example by dyeing or perming, as well as by the cleaning of the hair with shampoos and by environmental pollution, the importance of care products with the longest possible effect increases. Such care products affect the natural structure and properties of the hair. Thus, for example, after such treatments, the wet and dry combability of the hair, the hold and the fullness of the hair can be optimized or the hair can be protected from increased split ends.

It has therefore long been customary to subject the hair to a special aftertreatment. In this case, the hair is treated with special active ingredients, for example quaternary ammonium salts or special polymers, usually in the form of a rinse. Depending on the formulation, this treatment improves the combability, the hold and the fullness of the hair and reduces the split rate.

The use of special oligopeptides for the care of keratinic fibers is known, for example, from WO2010 / 026010 A1. In particular, oligopeptides with the sequence Tyr-Glu-Glu-Glu-Ile-Arg-Val-Leu are disclosed as particularly suitable for hair care.

Hyaluronic acid and its derivatives are popular ingredients in skin cosmetics. They are also being used increasingly in hair cosmetics. WO2009 / 080220 A1 discloses polysaccharides esterified at the hydroxyl function with glucosamine or galactoamine residues, which are e.g. selected from lipoic acid esterified hyaluronic acid. These substances have film-forming properties that strengthen the hair follicles and protect the hair against splitting and external influences from free radicals. In tests, improved softness, lightness, curl retention, and a reduction in brittleness have been demonstrated.

There is still the need to provide active ingredients or combinations of active ingredients for cosmetic products with good care properties and good biodegradability. Especially in dye-containing and / or electrolyte-containing formulations, there is a need for additional nourishing active ingredients which can be easily incorporated into known formulations and are not weakened in their action due to incompatibilities with other ingredients. It has now been found that hyaluronic acid esters and certain oligopeptides enhance their positive effect on the hair and the hair follicle.

A first subject of the present invention are hair treatment compositions containing - in each case based on their weight - a) 0.0001 to 10 wt .-% of at least one oligopeptide, the at least one Amino Acid Sequence Glu-Glu-Glu

wherein the amino group may be free or protonated and the carboxy groups may be free or deprotonated

b) from 0.0001 to 10% by weight of at least one ester of hyaluronic acid with lipoic acid,

Formic acid or mixtures thereof.

In this formula as well as in the formulas below, the parenthesized hydrogen atom of the amino group, as well as the bracketed hydroxy group of the acid function, means that the respective groups can be present as such (then it is an oligopeptide with the relevant number of amino acids as shown (see above) Formula 3) or that the amino acid sequence is present in an oligopeptide, which comprises even more amino acids - depending on where the other amino acid (s) is / are bound, the parenthetical components of the above formula by the / are the other Replaced amino acid residue (s).

Hair treatment compositions for the purposes of the present invention are, for example, hair shampoos, hair conditioners, conditioning shampoos, hairsprays, hair conditioners, hair treatments, hair wraps, hair tonics, perming solutions, hair dye shampoos, hair dyes, hair fixatives, hair dressings, hairstyling preparations, hair lotions, mousses, hair gels , Hair waxes or their combinations. In view of the fact that men often shy away from the use of several different agents and / or several application steps, agents according to the invention are preferably those agents which the man uses anyway. Preferred agents according to the invention are therefore shampoos, conditioners or hair tonics.

The hair treatment compositions according to the invention contain, by weight, 0.0001 to 10% by weight of at least one oligopeptide containing at least one amino acid residue Glu-Glu-Glu, i. has at least three consecutive glutamic acids.

Oligopeptides in the sense of the present application are acid amide-like linked by peptide bonds condensation products of amino acids comprising at least 3 and a maximum of 25 amino acids

In hair treatment agents preferred according to the invention, the oligopeptide comprises 5 to 15 Amino acids, preferably 6 to 13 amino acids, particularly preferably 7 to 12 amino acids and in particular 8, 9 or 10 amino acids.

Depending on whether further amino acids are bound to the sequence Glu-Glu-Glu and depending on the nature of these amino acids, the molecular weight of the oligopeptide contained in the agents of the invention may vary. Hair treatment compositions preferred according to the invention are characterized in that the oligopeptide has a molecular weight of from 650 to 3000 Da, preferably from 750 to 2500 Da, particularly preferably from 850 to 2000 Da and in particular from 1000 to 1600 Da. In summary, preferred hair treatment compositions according to the invention are characterized in that the oligopeptide comprises 5 to 15 amino acids, preferably 6 to 13 amino acids, more preferably 7 to 12 amino acids and especially 8, 9 or 10 amino acids and a molecular weight of 650 to 3000 Da, preferably 750 to 2500 Da, more preferably from 850 to 2000 Da and in particular from 1000 to 1600 Da.

As can be seen from the preferred number of amino acids in the oligopeptides and the preferred molecular weight range, it is preferred to use oligopeptides which do not consist solely of the three glutamic acids but have further amino acids bound to this sequence. These other amino acids are preferably selected from certain amino acids, while certain other representatives are less preferred in the present invention.

Thus, it is preferred if the oligopeptides used in the agents according to the invention contain no methionine.

It is further preferred if the oligopeptides used in the agents according to the invention contain no cysteine and / or cystine.

It is further preferred if the oligopeptides used in the agents according to the invention contain no aspartic acid and / or asparagine.

It is further preferred if the oligopeptides used in the agents according to the invention contain no serine and / or threonine.

In contrast, it is preferred if the oligopeptides used in the agents according to the invention contain tyrosine.

It is further preferred if the oligopeptides used in the agents according to the invention contain leucine.

It is further preferred if the oligopeptides used in the agents according to the invention contain isoleucine.

It is further preferred if the oligopeptides used in the agents according to the invention contain arginine.

It is further preferred if the oligopeptides used in the agents according to the invention contain valine.

Particularly preferred oligopeptides or contained in the preferred oligopeptides Amino acid sequences are described below:

A particularly preferred oligopeptide additionally contains tyrosine, which is preferably linked via its acid function to the Glu-Glu-Glu sequence. Hair treatment agents which are preferred according to the invention are therefore characterized in that the oligopeptide contained in them has at least one amino acid sequence Tyr-Glu-Glu-Glu, where the amino group can be free or protonated and the carboxy groups can be free or deprotonated.

Another particularly preferred oligopeptide additionally contains isoleucine, which is preferably linked to the Glu-Glu-Glu sequence via its amino function. Hair-treatment compositions which are preferred according to the invention are therefore characterized in that the oligopeptide contained in them has at least one amino acid sequence Glu-Glu-Glu-Ile, wherein the amino group can be free or protonated and the carboxy groups can be free or deprotonated.

Oligopeptides which have both the abovementioned amino acids (tyrosine and isoleucine) are preferred according to the invention. Hair treatment agents according to the invention in which the oligopeptide contained in them has at least one amino acid sequence Tyr-Glu-Glu-Glu-Ile are particularly preferred, the amino group being free or protonated and the carboxy groups being free or deprotonated.

Further preferred oligopeptides additionally contain arginine, which is preferably bound to isoleucine

Hair treatment composition according to one of claims 1 to 6, characterized in that the oligopeptide contained in them has at least one amino acid sequence Tyr-Glu-Glu-Glu-Ile-Arg, wherein the amino groups are free or protonated and the carboxy groups free or deprotonated may be present.

Still further preferred oligopeptides additionally contain valine, which is preferably bound to the arginine. Hair-treatment agents which are further preferred according to the invention are therefore characterized in that the oligopeptide contained in them has at least one amino acid sequence Tyr-Glu-Glu-Glu-Ile-Arg-Val, the amino groups being free or protonated and the carboxy groups being free or deprotonated can.

Still further preferred oligopeptides additionally contain leucine, which is preferably bound to the valine. Further preferred hair treatment compositions according to the invention are characterized in that the oligopeptide contained in them has at least one amino acid sequence Tyr-Glu-Glu-Glu-Ile-Arg-Val-Leu, wherein the amino groups are free or protonated and the carboxy groups are free or deprotonated may be present.

Particularly preferred oligopeptides additionally contain leucine, which is preferably bound to the tyrosine. Further preferred hair treatment compositions according to the invention are characterized in that the oligopeptide contained in them has at least one amino acid sequence Leu-Tyr-Glu-Glu-Glu-Ile-Arg-Val-Leu, wherein the amino groups are free or protonated and the Carboxy groups may be present freely or deprotonated.

Very particular preference is given to compositions according to the invention containing at least two oligopeptides which satisfy the abovementioned criteria but differ from one another. For example, hair treatment agents containing at least two mutually different oligopetides A and B, both containing the amino acid sequence Glu-Glu-Glu, are preferred.

Such mutually different oligopeptides A and B correspond to each other in that they carry three consecutive Glu amino acids in their amino acid sequence, but have differences in the upstream or downstream amino acids. Preference is given to mutually different peptides with partial agreement, which may well be greater than in the above-mentioned three amino acids.

Thus, further preferred hair treatment compositions are characterized in that they contain at least two mutually different oligopeptides A and B, both of which contain the amino acid sequence Glu-Glu-Glu-Ile.

Also preferred are hair treatment agents containing at least two mutually different oligopeptides A and B, both containing the amino acid sequence Tyr-Glu-Glu-Glu.

Still further preferred hair treatment agents are characterized by containing at least two mutually different oligopetides A and B, both containing the amino acid sequence Glu-Glu-Glu-Ile-Arg.

Even more preferred hair treatment agents contain at least two mutually different oligopetides A and B, both containing the amino acid sequence Tyr-Glu-Glu-Glu-Ile. Very particularly preferred hair treatment compositions are characterized in that they contain at least two mutually different oligopeptides A and B, both of which contain the amino acid sequence Glu-Glu-Glu-Ile-Arg.

Also most particularly preferred hair treatment agents contain at least two mutually different oligopetides A and B, both containing the amino acid sequence Tyr-Glu-Glu-Glu-Ile-Arg.

Preferably, there is an even greater structural match in the oligopeptides. Thus, hair treatment compositions containing at least two distinct oligopetides A and B, both of which contain the amino acid sequence Glu-Glu-Glu-Ile-Arg-Val, are further preferred embodiments of the present invention.

Also preferred embodiments are hair treatment compositions containing at least two mutually different oligopeptides A and B, both of which contain the amino acid sequence Tyr-Glu-Glu-Glu-Ile-Arg-Val.

Still further preferred hair treatment compositions according to the invention contain at least two mutually different oligopetides A and B, both of which contain the amino acid sequence Glu-Glu-Glu-Ile-Arg-Val-Leu. Also, even more preferred hair treatment agents contain at least two mutually different oligopetides A and B, both containing the amino acid sequence Tyr-Glu-Glu-Glu-Ile-Arg-Val-Leu.

Particularly preferred hair treatment agents are characterized in that they contain at least two mutually different oligopetides A and B, wherein the oligopeptide A has the amino acid sequence Leu-Tyr-Glu-Glu-Glu-Ile-Arg-Val-Leu, wherein the amino groups are free or protonated and the carboxy groups may be free or deprotonated and the oligopeptide B has the amino acid sequence Tyr-Glu-Glu-Glu-Ile-Arg-Val-Leu, wherein the amino groups are free or protonated and the carboxy groups are free or may be present deprotonated.

Very particularly preferred agents of this last-mentioned embodiment contain, based on the weight of the composition, 0.00001 to 1% by weight of oligopeptide A and 0.00001 to 1% by weight of oligopeptide B.

Further preferred agents of this last-mentioned embodiment contain -0.00005 to 0.1% by weight of oligopeptide A and 0.00005 to 0.1% by weight of oligopeptide B, based on the weight of the agent.

Still further preferred agents of this latter embodiment contain, based on the weight of the agent, from 0.0001 to 0.01% by weight of oligopeptide A and from 0.0001 to 0.001% by weight of oligopeptide B.

It has been found that the use of the abovementioned oligopeptides imparts outstanding properties to the hair treatment compositions according to the invention. The compositions of the invention impart more resilience to the hairs treated with them, resulting in higher tensile strengths of the keratin fibers and a reduction in elasticity loss, e.g. when damaged by atmospheric agents. In particular, the particularly preferred oligopeptides also stabilize the moisture balance of the keratinic fibers, so that the combability improves and the aging process is delayed.

Another advantage of the compositions of the invention is that the moldability and restructurability of keratinic fibers treated with them is improved.

The oligopeptides used in the context of the present invention, which satisfy the abovementioned conditions, can advantageously be obtained from keratinic materials. It is preferred according to the invention that these oligopeptides are used in high proportions, based on the total keratinic peptide content of the agents.

It is very particularly preferred for the highest possible proportion of all the keratinic peptides contained in the agent to satisfy the abovementioned conditions.

Preferred hair treatment agents according to the invention are characterized in that at least 0.1% by weight, preferably at least 0.5% by weight, particularly preferably at least 1% by weight, more preferably at least 2.5% by weight, even more preferred at least 5% by weight and in particular at least 10% by weight of all the keratinic peptides contained in the composition Have amino acid sequence Glu-Glu-Glu.

Further preferred hair treatment compositions according to the invention are characterized in that at least 0.1 wt .-%, preferably at least 0.5 wt .-%, particularly preferably at least 1 wt .-%, more preferably at least 2.5 wt .-%, even further preferably at least 5% by weight and in particular at least 10% by weight of all the keratinic peptides contained in the middle have the amino acid sequence Glu-Glu-Glu-Ile.

Still further preferred hair treatment compositions according to the invention are characterized in that at least 0.1 wt .-%, preferably at least 0.5 wt .-%, particularly preferably at least 1 wt .-%, more preferably at least 2.5 wt .-%, still more preferably at least 5% by weight and in particular at least 10% by weight of all the keratinic peptides contained in the middle have the amino acid sequence Tyr-Glu-Glu-Glu.

Particularly preferred hair treatment compositions according to the invention are characterized in that at least 0.1% by weight, preferably at least 0.5% by weight, more preferably at least 1% by weight, more preferably at least 2.5% by weight, still further preferably at least 5% by weight and in particular at least 10% by weight of all the keratinic peptides contained in the middle have the amino acid sequence Tyr-Glu-Glu-Glu-Ile.

Very particularly preferred hair treatment compositions according to the invention are characterized in that at least 0.1% by weight, preferably at least 0.5% by weight, more preferably at least 1% by weight, more preferably at least 2.5% by weight, still more preferably at least 5% by weight and in particular at least 10% by weight of all the keratinic peptides contained in the middle have the amino acid sequence Tyr-Glu-Glu-Glu-Ile-Arg.

Still further preferred hair treatment compositions according to the invention are characterized in that at least 0.1 wt .-%, preferably at least 0.5 wt .-%, particularly preferably at least 1 wt .-%, more preferably at least 2.5 wt .-%, still more preferably at least 5% by weight and in particular at least 10% by weight of all the keratinic peptides contained in the middle have the amino acid sequence Tyr-Glu-Glu-Glu-Ile-Arg-Val.

Particularly preferred hair treatment compositions according to the invention are characterized in that at least 0.1% by weight, preferably at least 0.5% by weight, more preferably at least 1% by weight, more preferably at least 2.5% by weight, still further preferably at least 5% by weight and in particular at least 10% by weight of all the keratinic peptides contained in the middle have the amino acid sequence Tyr-Glu-Glu-Glu-Ile-Arg-Val-Leu.

The abovementioned conditions relate to the total content of the agents according to the invention to peptides which originate from keratinic materials. In addition to the oligopeptides of keratinic origin, of course, other peptides and / or protenihydrolysates can be used, for example from other native sources. For example, the additional use of wheat protein hydrolysates is preferred, see below. The hair treatment compositions according to the invention contain as the second essential ingredient - based on their weight - 0.0001 to 10 wt .-% of at least one ester of hyaluronic acid with lipoic acid, formic acid or mixtures thereof.

The agents according to the invention may accordingly contain esters of hyaluronic acid with lipoic acid, esters of hyaluronic acid with formic acid or mixed esters of hyaluronic acid with lipoic acid and formic acid. The latter are particularly preferred in view of their effectiveness in the combination according to the invention.

Hair treatment agents preferred according to the invention are characterized in that they contain 0.0005 to 7.5% by weight, preferably 0.001 to 6% by weight, more preferably 0.005 to 5% by weight, more preferably 0.01 to 4% by weight. % and in particular 0.1 to 3 wt .-% of at least one ester of hyaluronic acid with lipoic acid, formic acid or mixtures thereof of the formula (I)

in the

X is selected from H, Na and K,

- n stands for numbers from 100 to 10000, and

R1, R2, R3 and R4 are independently selected from -H, -C (0) -H and

with the proviso that at least one of R1, R2, R3 and R4 is other than -H.

The hyaluronic acid has 4 esterifiable hydroxyl groups, so that, based on the individual repeating unit, the following hyaluronic acid esters can be used according to the invention:

Hyaluronic acid esters in which an OH group is esterified with lipoic acid,

Hyaluronic acid esters in which two OH groups are esterified with lipoic acid,

Hyaluronic acid esters in which three OH groups are esterified with lipoic acid,

Hyaluronic acid esters in which four OH groups are esterified with lipoic acid,

Hyaluronic acid esters in which an OH group is esterified with formic acid,

Hyaluronic acid esters in which two OH groups are esterified with formic acid,

Hyaluronic acid esters in which three OH groups are esterified with formic acid, Hyaluronic acid esters in which four OH groups are esterified with formic acid,

Hyaluronic acid esters in which an OH group is esterified with lipoic acid and an OH group with formic acid,

Hyaluronic acid esters in which one OH group is esterified with lipoic acid and two OH groups with formic acid,

Hyaluronic acid esters in which one OH group is esterified with lipoic acid and three OH groups with formic acid,

Hyaluronic acid esters in which two OH groups are esterified with lipoic acid and one OH group with formic acid,

Hyaluronic acid esters in which two OH groups are esterified with lipoic acid and two OH groups with formic acid,

Hyaluronic acid esters in which three OH groups with lipoic acid and one OH group with

Formic acid are esterified.

The esterification takes place statistically, so that individual monomer units can remain completely unesterified. It is inventively preferred if a certain part of the esterifiable OH groups is esterified with lipoic acid, regardless of how they are distributed to the hyaluronic acid molecule.

Hair treatment agents preferred according to the invention are characterized in that the degree of esterification of the OH groups with lipoic acid is 0.1 to 0.5 mol / mol, preferably 0.125 to 0.45 mol / mol, more preferably 0.2 to 0.4 mol / mol, even more preferably 0.25 to 0.35 mol / mol and in particular 0.27 to 0.33 mol / mol. In other words, most preferably 27 to 33 OH groups are esterified with lipoic acid on 25 repetition units (with 100 OH groups).

It is further preferred according to the invention if a certain part of the esterifiable OH groups is esterified with formic acid, likewise irrespective of how they are distributed over the hyaluronic acid molecule.

Hair treatment agents which are preferred according to the invention are characterized in that the degree of esterification of the OH groups with formic acid is 0.001 to 0.5 mol / mol, preferably 0.002 to 0.4 mol / mol, more preferably 0.005 to 0.3 mol / mol, even more preferably 0 , 0075 to 0.25 mol / mol and in particular 0.01 to 0.2 mol / mol. In other words, most preferably one to 20 OH groups are esterified with formic acid to 25 repeating units (having 100 OH groups).

It is extremely preferable that both conditions are satisfied at the same time. Particularly preferred hair treatment compositions according to the invention are characterized in that the degree of esterification of the OH groups with lipoic acid is 0.1 to 0.5 mol / mol, preferably 0.125 to 0.45 mol / mol, more preferably 0.2 to 0.4 mol / mol , even more preferably 0.25 to 0.35 mol / mol and in particular 0.27 to 0.33 mol / mol and the degree of esterification of the OH groups with formic acid 0.001 to 0.5 mol / mol, preferably 0.002 to 0.4 mol / mol, more preferably 0.005 to 0.3 mol / mol, even more preferably 0.0075 to 0.25 mol / mol and in particular 0.01 to 0.2 mol / mol. In other words, most preferably 27 to 33 OH groups are esterified with lipoic acid and one to 20 OH groups are esterified with formic acid over 25 repetition units (with 100 OH groups).

As already mentioned, it is preferred to use hyaluronic acid esters in which 27 to 33 OH groups are esterified with lipoic acid on 25 repeating units (having 100 OH groups). Accordingly, preferred hair treatment compositions contain from 0.0005 to 7.5% by weight, preferably from 0.001 to 6% by weight, more preferably from 0.005 to 5% by weight, more preferably from 0.01 to 4% by weight and in particular 0, 1 to 3 wt .-% of at least one ester of hyaluronic acid with lipoic acid having at least one recurring unit of the formula (II)

in the

X is selected from H, Na and K,

n stands for numbers from 1 to 10000, and

R1, R2 and R3 are independently selected from -H, -C (0) -H and

Further preferred hair treatment compositions according to the invention contain 0.0005 to 7.5 wt .-%, preferably 0.001 to 6 wt .-%, more preferably 0.005 to 5 wt .-%, more preferably 0.01 to 4 wt .-% and in particular 0 , 1 to 3% by weight of at least one ester of hyaluronic acid with lipoic acid of the formula (IIa)

in the

X is selected from H, Na and K,

n and m are numbers from 100 to 10000, and

R1, R2, R3 and R4 are independently selected from -H, -C (0) -H and

In the formula (IIa), the recurring units with the indices n and m need not necessarily be bound together as a block, but rather they may be present in a statically distributed manner over the entire molecule.

Still further preferred hair treatment compositions according to the invention contain from 0.0005 to 7.5 wt .-%, preferably 0.001 to 6 wt .-%, more preferably 0.005 to 5 wt .-%, more preferably 0.01 to 4 wt .-% and in particular 0.1 to 3% by weight of at least one ester of hyaluronic acid with lipoic acid of the formula (IIb)

(IIb), in the X is selected from H, Na and K,

n, m and o stand for numbers from 100 to 10000, and

R1, R2, R3 and R4 are independently selected from -H, -C (0) -H and

Here, too, in the formula (IIb), the recurring units with the indices n, m and o need not necessarily be bound together as a block, but rather they can be present in a statically distributed manner over the entire molecule.

Also preferred hair treatment compositions according to the invention contain 0.0005 to 7.5 wt .-%, preferably 0.001 to 6 wt .-%, more preferably 0.005 to 5 wt .-%, more preferably 0.01 to 4 wt .-% and in particular 0 , 1 to 3 wt .-% of at least one ester of hyaluronic acid with lipoic acid having at least one recurring unit of the formula (III)

in the

X is selected from H, Na and K,

n stands for numbers from 1 to 10000, and

R1, R2 and R4 are independently selected from -H, -C (O) -H and

Further preferred hair treatment compositions according to the invention contain 0.0005 to 7.5 wt .-%, preferably 0.001 to 6 wt .-%, more preferably 0.005 to 5 wt .-%, more preferably 0.01 to 4 wt .-% and in particular 0 , 1 to 3% by weight of at least one ester of hyaluronic acid with lipoic acid of the formula (IIIa)

in the

X is selected from H, Na and K,

n and m are numbers from 100 to 10000, and

R1, R2, R3 and R4 are independently selected from -H, -C (0) -H and

In the formula (IIIa), the repeating units with the indices n and m do not necessarily have to be bound together as a block; rather, they can be statically distributed over the entire molecule.

Still further preferred hair treatment compositions according to the invention contain from 0.0005 to 7.5 wt .-%, preferably 0.001 to 6 wt .-%, more preferably 0.005 to 5 wt .-%, more preferably 0.01 to 4 wt .-% and in particular 0.1 to 3% by weight of at least one ester of hyaluronic acid with lipoic acid of the formula (IIIb)

X is selected from H, Na and K,

n, m and o stand for numbers from 100 to 10000, and

R1, R2, R3 and R4 are independently selected from -H, -C (0) -H and

Here, too, in the formula (IIIb), the repeating units with the indices n, m and o do not necessarily have to be bound together as a block, but rather they can be present in a statically distributed manner over the entire molecule.

Also preferred hair treatment compositions according to the invention contain 0.0005 to 7.5 wt .-%, preferably 0.001 to 6 wt .-%, more preferably 0.005 to 5 wt .-%, more preferably 0.01 to 4 wt .-% and in particular 0 , 1 to 3 wt .-% of at least one ester of hyaluronic acid with lipoic acid having at least one recurring unit of the formula (IV)

in the

X is selected from H, Na and K,

n stands for numbers from 1 to 10000, and

R1, R3 and R4 are independently selected from -H, -C (0) -H and

Further preferred hair treatment compositions according to the invention contain 0.0005 to 7.5 wt .-%, preferably 0.001 to 6 wt .-%, more preferably 0.005 to 5 wt .-%, more preferably 0.01 to 4 wt .-% and in particular 0 , 1 to 3% by weight of at least one ester of hyaluronic acid with lipoic acid of the formula (IVa)

in the

X is selected from H, Na and K,

n and m are numbers from 100 to 10000, and

R1, R2, R3 and R4 are independently selected from -H, -C (0) -H and

In the formula (IVa), the repeating units with the indices n and m do not necessarily have to be bound together as a block, but rather they can be present in a statically distributed manner over the entire molecule.

Still further preferred hair treatment compositions according to the invention contain from 0.0005 to 7.5 wt .-%, preferably 0.001 to 6 wt .-%, more preferably 0.005 to 5 wt .-%, more preferably 0.01 to 4 wt .-% and in particular 0.1 to 3% by weight of at least one ester of hyaluronic acid with lipoic acid of the formula (IVb)

(IVb), in the X is selected from H, Na and K,

n, m and o stand for numbers from 100 to 10000, and

R1, R2, R3 and R4 are independently selected from -H, -C (0) -H and

Again, in the formula (IVb), the repeating units with the indices n, m and o need not necessarily be bound as a block to each other, but they may be statically distributed over the entire molecule.

Also preferred hair treatment compositions according to the invention contain 0.0005 to 7.5 wt .-%, preferably 0.001 to 6 wt .-%, more preferably 0.005 to 5 wt .-%, more preferably 0.01 to 4 wt .-% and in particular 0 , 1 to 3 wt .-% of at least one ester of hyaluronic acid with lipoic acid having at least one recurring unit of the formula (V)

in the

X is selected from H, Na and K,

n stands for numbers from 1 to 10000, and

R2, R3 and R4 are independently selected from -H, -C (0) -H and

Further preferred hair treatment compositions according to the invention contain 0.0005 to 7.5 wt .-%, preferably 0.001 to 6 wt .-%, more preferably 0.005 to 5 wt .-%, more preferably 0.01 to 4 wt .-% and in particular 0 , 1 to 3 wt .-% of at least one ester of hyaluronic acid with Ionic acid of formula (Va)

(Va), in the

X is selected from H, Na and K,

n and m are numbers from 100 to 10000, and

R1, R2, R3 and R4 are independently selected from -H, -C (0) -H and

In the formula (Va), the recurring units with the indices n and m need not necessarily be bound together as a block, but rather they may be present in a statically distributed manner over the entire molecule.

Still further preferred hair treatment compositions according to the invention contain from 0.0005 to 7.5 wt .-%, preferably 0.001 to 6 wt .-%, more preferably 0.005 to 5 wt .-%, more preferably 0.01 to 4 wt .-% and in particular 0.1 to 3% by weight of at least one ester of hyaluronic acid with lipoic acid of the formula (Vb)

(Vb), in the X is selected from H, Na and K,

n, m and o stand for numbers from 100 to 10000, and

R1, R2, R3 and R4 are independently selected from -H, -C (0) -H and

Here, too, in the formula (Vb), the recurring units with the indices n, m and o do not necessarily have to be bound together as a block; rather, they can be present in a statically distributed manner over the entire molecule.

As already mentioned, it is preferred to use hyaluronic acid esters in which one to 20 OH groups are esterified with formic acid to 25 repeating units (having 100 OH groups). Accordingly, preferred hair treatment compositions contain from 0.0005 to 7.5% by weight, preferably from 0.001 to 6% by weight, more preferably from 0.005 to 5% by weight, more preferably from 0.01 to 4% by weight and in particular 0, 1 to 3 wt .-% of at least one ester of hyaluronic acid with formic acid having at least one recurring unit of the formula (VI)

in the

X is selected from H, Na and K,

- n stands for numbers from 100 to 10000, and

R1, R2 and R3 are independently selected from -H, -C (0) -H and

The agents according to the invention may contain further active ingredients and adjuvants. These are described below.

Preferably, the inventive compositions additionally contain at least one emulsifier or a surfactant, wherein surface-active substances depending on the field of application as surfactants or as Emulsifiers are selected and selected from anionic, cationic, zwitterionic, ampholytic and nonionic surfactants and emulsifiers.

According to the invention preferred hair treatment compositions are characterized in that they - based on its weight - 0.5 to 70 wt .-%, preferably 1 to 60 wt .-% and in particular 5 to 25 wt .-% of anionic (s) and / or nonionic (s) and / or cationic and / or amphoteric surfactant (s).

Suitable anionic surfactants and emulsifiers for the compositions according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. As a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule.

Zwitterionic surfactants and emulsifiers are surface-active compounds which carry in the molecule at least one quaternary ammonium group and at least one -COO < ⁾ or -SO 3 ⁽⁾ group. Particularly suitable zwitterionic surfactants and emulsifiers are the so-called betaines, such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3 carboxymethyl-3-hydroxyethyl imidazolines having in each case 8 to 18 carbon atoms in the alkyl or acyl group and the coco acylaminoethylhydroxyethyl carboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants and emulsifiers are understood as meaning those surface-active compounds which, apart from a Cs-C24-alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -SO 3 H-group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylaminopropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 24 C Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C 12 -C 18 acyl sarcosine.

Nonionic surfactants and emulsifiers contain as hydrophilic group z. A polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups.

Very particular preference is given to compositions according to the invention which additionally contain fatty alcohol (s) and / or fatty alcohol alkoxylate (s), preferably C 12-22 fatty alcohol (s) and / or C 12-22 fatty alcohol ethoxylate (s) having 10 to 30 EO units, especially preferably C 16-18 fatty alcohol (s) and / or C 16-18 fatty alcohol ethoxylate (s) having 12 to 20 EO units, preferably in amounts of from 5 to 20% by weight, preferably from 7.5 to 17.5% by weight and in particular from 10 to 15% by weight, based in each case on the weight of the composition.

In summary, hair-treatment compositions according to the invention are preferred which contain, by weight, from 0.1 to 20% by weight, preferably from 0.25 to 17.5% by weight and in particular from 5 to 15% by weight of anionic surfactant ( e), particularly preferably fatty alcohol ether sulfates of the formula

H3C- (CH ₂₎ n- (OCH ₂ CH 2) k-OS03- M ⁺

in which n represents values of from 5 to 21, preferably from 7 to 19, more preferably from 9 to 17 and in particular from 11 to 13 and k for values of 1, 2, 3, 4, 5, 6, 7, 8 , 9 or 10, preferably 1, 2 or 3 and especially 2, and M is a cation from the group Na ⁺ , K ⁺ NHV, Vi Mg ²⁺ , Vi Zn ²⁺ , preferably Na ⁺ .

As a further optional constituent, the agents according to the invention may contain from 0.01 to 10% by weight of at least one polymer from the group of cationic and / or amphoteric polymers.

Cationic or amphoteric polymers are to be understood as meaning polymers which have a group in the main and / or side chain which may be "temporary" or "permanent" cationic. According to the invention, "permanently cationic" refers to those polymers which have a cationic group, irrespective of the pH of the agent. These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic groups are quaternary ammonium groups. In particular, those polymers in which the quaternary ammonium group is bonded via a C1-C4 hydrocarbon group to a polymer main chain constructed from acrylic acid, methacrylic acid or derivatives thereof have proven to be particularly suitable.

In addition to cationic polymers or in their place, the agents according to the invention can also contain amphoteric polymers. These additionally have at least one negatively charged group in the molecule and are also referred to as zwitterionic polymers.

Preferably, the polymer or polymers are used within narrower ranges. Thus, agents according to the invention are preferred which, based on their weight, are from 0.05 to 7.5% by weight, preferably from 0.1 to 5% by weight, more preferably from 0.2 to 3.5% by weight and in particular from 0.25 to 2.5% by weight of amphoteric polymer (s).

Regardless of whether the agents contain amphoteric polymers or not, further preferred agents according to the invention are characterized in that they contain, based on their weight, from 0.05 to 7.5% by weight, preferably from 0.1 to 5% by weight. -%, particularly preferably 0.2 to 3.5 wt .-% and in particular 0.25 to 2.5 wt .-% cationic (s) polymer (s) included.

In addition to the cationic polymers or in their place, the agents of the invention may contain amphoteric polymers. As a further ingredient, the agents according to the invention may with particular preference contain one or more amino acids. Particularly preferred amino acids which can be used according to the invention are from the group glycine, alanine, valine, leucine, isoleucine, phenylalanine, tyrosine, tryptophan, proline, aspartic acid, glutamic acid, asparagine, glutamine, serine, threonine, cysteine, methionine, lysine, arginine, histidine, β Alanine, 4-aminobutyric acid (GABA), betaine, L-cystine (L-Cyss), L-carnitine, L-citrulline, L-theanine, 3 ', 4'-dihydroxy-L-phenylalanine (L-dopa), 5'-hydroxy-L-tryptophan, L-homocysteine, S-methyl-L-methionine, S-allyl-L-cysteine-sulfoxide (L-alliin), L-iran-4-hydroxyproline, L-5-oxoproline ( L-pyroglutamic acid), L-phosphoserine, creatine, 3-methyl-L-histidine, L-ornithine, whereby both the individual amino acids and mixtures can be used.

Preferred agents according to the invention contain one or more amino acids in narrower quantitative ranges. Here, preferred hair treatment compositions according to the invention are characterized in that they contain as care substance - based on their weight - 0.01 to 5 wt .-%, preferably 0.02 to 2.5 wt .-%, particularly preferably 0.05 to 1, 5 Wt .-%, more preferably 0.075 to 1 wt .-% and in particular 0.1 to 0.25 wt .-% amino acid (s), preferably from the group of glycine and / or alanine and / or valine and / or lysine and / or leucine and / or threonine.

The compositions according to the invention may furthermore contain all active substances, additives and auxiliaries known for such preparations. In many cases, the agents contain at least one surfactant, wherein in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proved to be advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants. These surfactants have been described in detail above.

In a further preferred embodiment, the agents according to the invention may contain emulsifiers (F). Emulsifiers effect at the phase interface the formation of water- or oil-stable adsorption layers, which protect the dispersed droplets against coalescence and thus stabilize the emulsion. Emulsifiers are therefore constructed like surfactants from a hydrophobic and a hydrophilic part of the molecule. Hydrophilic emulsifiers preferably form O / W emulsions and hydrophobic emulsifiers preferably form W / O emulsions. An emulsion is to be understood as meaning a droplet-like distribution (dispersion) of a liquid in another liquid under the expense of energy in order to create stabilizing phase interfaces by means of surfactants. The selection of these emulsifying surfactants or emulsifiers depends on the substances to be dispersed and the respective outer phase and the fineness of the emulsion. Finally, the compositions according to the invention may also contain plant extracts (L).

Usually these extracts are produced by extraction of the whole plant. However, in individual cases it may also be preferred to prepare the extracts exclusively from flowers and / or leaves of the plant.

A particularly preferred group of ingredients are the silicones. Particularly preferred compositions according to the invention comprise the silicone (s) preferably in amounts of from 0.1 to 10% by weight, preferably from 0.25 to 7% by weight and in particular from 0.5 to 5% by weight. , in each case based on the total mean.

Preferred silicones are described below.

Particularly preferred agents according to the invention are characterized in that they contain at least one silicone of the formula Si-I

(CH ₃ ) 3 Si - [0-Si (CH ₃ ) 2] x -O-Si (CH ₃ ) 3 (Si-I),

in which x is a number from 0 to 100, preferably from 0 to 50, more preferably from 0 to 20 and in particular 0 to 10.

These silicones are called DIMETHICONE according to the INCI nomenclature.

Preferred silicones which can be used according to the invention have viscosities of from 0.2 to 2 mm ² s at 20 ° C., silicones having viscosities of from 0.5 to 1 mm ² s being particularly preferred.

Particularly preferred agents according to the invention contain one or more amino-functional

Silicones. Such silicones may e.g. through the formula

M (RaQbSiO (4-a-b) / 2) x (rosio (4-o) / 2) y M

wherein R in the above formula is a hydrocarbon or a hydrocarbon radical having 1 to about 6 carbon atoms, Q is a polar radical of the general formula -R HZ, wherein R is a divalent linking group attached to hydrogen and the radical Z. Z is an organic, amino-functional radical containing at least one amino-functional group; "a" assumes values in the range of about 0 to about 2, "b" assumes values in the range of about 1 to about 3, "a" + "b" is less than or equal to 3, and "c" is a number in the range from about 1 to about 3, and x is a number ranging from 1 to about 2,000, preferably from about 3 to about 50, and most preferably from about 3 to about 25, and y is a number ranging from about 20 to about 10,000 , preferably from about 125 to about 10,000, and most preferably from about 150 to about 1,000, and M is a suitable silicone end group as known in the art, preferably trimethylsiloxy. Non-limiting examples of the groups represented by R include alkyl groups such as methyl, ethyl, propyl, isopropyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, isohexyl and the like; Alkenyl radicals such as vinyl, halovinyl, alkylvinyl, allyl, haloallyl, alkylallyl; Cycloalkyl radicals such as cyclobutyl, cyclopentyl, cyclohexyl and the like; Phenyl radicals, benzyl radicals, halohydrocarbon radicals such as 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl, chlorophenyl and the like, and sulfur containing radicals such as mercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl and the like; preferably R is an alkyl radical containing from 1 to about 6 carbon atoms, and most preferably R is methyl. Examples of R include methylene, ethylene, propylene, hexamethylene, decamethylene, -CH 2 CH (CH 3) CH 2 -, phenylene, Naphthylene, -CH ₂ CH ₂ SCH ₂ CH ₂ , -CH ₂ CH ₂ OCH ₂ -, -OCH ₂ CH ₂ -, -OCH ₂ CH ₂ CH ₂ -, -CH ₂ CH (CH 3) C (O) ₂ -, - (CH ₂ ) ₃ CC (O) ₂ CH ₂ - , -C ₆ H ₄ C ₆ H4, -C ₆ H 4CH2C6H4-; and - (CH

Z is an organic, amino-functional radical containing at least one functional amino group. A possible formula for Z is NH (CH 2) z NH 2, wherein z is 1 or more. Another possible formula for Z is -NH (CH 2) z (CH 2) zzNH, wherein both z and zz are independently 1 or more, this structure comprising diamino ring structures, such as piperazinyl. Z is most preferably a -NHCH 2 CH 2 NH 2 radical. Another possible formula for Z is --N (CH 2) z (CH 2) zzNX 2 or --NX 2, wherein each X of X 2 is independently selected from the group consisting of hydrogen and alkyl groups of 1 to 12 carbon atoms, and zz is 0.

Q is most preferably a polar amine-functional radical of the formula -CH 2 CH 2 CH 2 NHCH 2 CH 2 NH 2. In the formulas, "a" assumes values in the range of about 0 to about 2, "b" assumes values in the range of about 2 to about 3, "a "+" b "is less than or equal to 3, and" c "is a number in the range of about 1 to about 3. the molar ratio of R _a Q b SiO _(4-a-b) / 2 units to R _c SiO (4- _C ) / 2 units range from about 1: 2 to 1:65, preferably from about 1: 5 to about 1:65, and most preferably from about 1:15 to about 1:20 One or more silicones of the above formula may be used, then the various variable substituents in the above formula may be different for the various silicone components present in the silicone blend.

Preferred agents according to the invention are characterized in that they contain an amino-functional silicone of the formula (Si-II)

R'aG ₃ - _a -Si (OSiG ₂ ) n - (OSiG _b R ' ₂ - _b ) m -O-SiG 3 -a-R' _a (Si-II),

contain, in which means:

G is -H, a phenyl group, -OH, -O-CH ₃ , -CH ₃ , -O-CH ₂ CH ₃ , -CH ₂ CH ₃ , -O-CH ₂ CH ₂ CH ₃ , -

CH ₂ CH ₂ CH ₃ , -O-CH (CH ₃ ) 2, -CH (CH ₃ ) ₂ , -O-CH ₂ CH ₂ CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , -O- CH ₂ CH (CH ₃ ) 2, -CH ₂ CH (CH ₃ ) 2, -0-CH (CH ₃₎ CH ₂ CH 3, -CH (CH ₃₎ CH ₂ CH 3, -0-C (CH ₃₎ _3, - C (CH ₃₎ _3;

a is a number between 0 and 3, in particular 0;

b is a number between 0 and 1, in particular 1,

m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n is preferably values from 0 to 1999 and in particular from 49 to 149 and m preferably values from 1 to 2000, in particular from 1 to 10,

- R ^' is a monovalent radical selected from

o -QN (R ") - CH ₂ -CH ₂ -N (R") 2

o -QN (R ") ₂

o -QN ⁺ (R ") ₃ A- o -QN ⁺ H (R ") ₂ A- o -QN ⁺ H ₂ (R") A- o -QN (R ") - CH 2 -CH ₂ -N ⁺ R" H ₂ A-,

wherein each Q is a chemical bond, -CH ₂ -, -CH ₂ -CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -C (CH ₃ ) 2, - CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ C (CH ₃ ) 2, -CH ( CH ₃ ) CH ₂ CH ₂ -,

R "is identical or different radicals from the group -H, -phenyl, -benzyl, -CH ₂ -CH (CH ₃ ) Ph, the Ci-20-alkyl radicals, preferably -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ H ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C (CH ₃ ) ₃ , and A represents an anion, which is preferably selected from chloride, bromide, iodide or methosulfate.

Particularly preferred agents according to the invention are characterized in that they contain at least one amino-functional silicone of the formula (Si-IIa)

(CH ₃ ) ₃ Si [0-Si (CH ₃ ) ₂ ] n [OSi (CH ₃ )] _m -OSi (CH ₃ ) ₃ (Si-Ia),

CH ₂ CH (CH ₃ ) CH ₂ NH (CH ₂ ) 2 NH 2

in which m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n preferably values of 0 to 1999 and in particular of 49 to 149 and m preferably values of 1 to 2000 , in particular from 1 to 10 assumes.

These silicones are referred to as trimethylsilylamodimethicones according to the INCI declaration.

Particular preference is also given to compositions according to the invention which are an amino-functional silicone of the formula (Si-IIb)

R- [Si _(CH3) 2-0] ni [Si (R) -0] m- [Si (CH ₃₎ _2] n2-R (Si-IIb),

wherein R is -OH, -O-CH ₃ or a -CH ₃ group and m, n1 and n2 are numbers whose

Sum (m + n1 + n2) between 1 and 2000, preferably between 50 and 150, wherein the

Sum (n1 + n2) preferably values from 0 to 1999 and in particular from 49 to 149 and m preferably values from 1 to 2000, in particular from 1 to 10 assumes.

These silicones are referred to as amodimethicones according to the INCI declaration.

Regardless of which amino-functional silicones are used, are inventive

Preferred are those which contain an amino-functional silicone whose amine number is above 0.25 meq / g, preferably above 0.3 meq / g and in particular above 0.4 meq / g. The

Amine number stands for the milliequivalents of amine per gram of aminofunktioinelen silicone. It can be determined by titration and also expressed in mg KOH / g. Agents preferred according to the invention are characterized in that, based on their weight, they contain 0.01 to 10% by weight, preferably 0.1 to 8% by weight, particularly preferably 0.25 to 7.5% by weight and in particular 0, 5 to 5 wt.% Amino-functional silicone (s) included.

The INCI CYCLOMETHICONE designated cyclic dimethicones are inventively used with preference. Here, agents according to the invention are preferred which contain at least one silicone of the formula Si-III

TO-Si (CH ₃ ) 2lx- (Si-II) in which x is a number from ό to 2ΌΌ, preferably from 3 to 10, more preferably from 30 to 7 and especially 3, 4, 5 or 6, stands ,

The silicones described above have a backbone composed of -Si-O-Si units. Of course, these Si-O-Si units may also be interrupted by carbon chains. Appropriate molecules are accessible by chain extension reactions and are preferably used in the form of silicone-in-water emulsions.

Agents which are likewise preferred according to the invention are characterized in that they contain at least one silicone of the formula Si-IV

R ₃ Si [0-SiR 2] x- (CH ₂ ) n- [0-SiR 2] _y -O-SiR ₃ (Si-IV),

in which R is identical or different radicals from the group -H, -phenyl, -benzyl, -CH 2 -CH (CH ₃ ) Ph, the Ci-20-alkyl radicals, preferably -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) 2, -CH ₂ CH ₂ CH 2 H 3, -CH ₂ CH (CH ₃ ) 2, -CH (CH ₃ ) CH ₂ CH ₃ , -C (CH ₃ ) ₃ , x and y represent a number of 0 to 200, preferably from 0 to 10, more preferably from 0 to 7 and in particular 0, 1, 2, 3, 4, 5 or 6, and n is a number from 0 to 10, preferably from 1 to 8 and in particular stands for 2, 3, 4, 5, 6.

The silicones are preferably water-soluble. Agents preferred according to the invention are characterized in that they contain at least one water-soluble silicone.

For aesthetic reasons, "clear" products are often preferred by consumers, hair treatment agents which are preferred according to the invention are therefore transparent or translucent, transparent or translucent in the context of the present invention means a composition which has an NTU value of less than or equal to 100. The NTU value (Nephelometrie Turbidity Unit) is a fluid turbidity measurement unit used in water treatment and is the unit of fluid turbidity measured with a calibrated nephelometer. The compositions according to the invention have advantageous properties and also confer advantageous properties on the hair treated with them. In particular, in hair and scalp treatment benefits have been observed bvzw the advantages of the oligopeptides. Hyaluronic acid ester go out alone. Thus, hair treatment compositions according to the invention increase the elasticity of the hair treated with them and lead to an inner-structural strengthening of the hair fibers, which is reflected, for example, in higher melting temperatures in differential thermal analysis.

It also shows an improvement in wet and dry combing and prevention of premature splitting in the treated hair. On the skin and in particular the scalp, the compositions according to the invention cause an increase in the elasticity and, surprisingly, sebum-regulating effects. The visual impression of "greasy" skin or hair is thus avoided or weakened.

Another object of the present invention is a method for improving at least one of the properties

Tensile strength of keratinic fibers, especially human hair; Stabilizing the moisture balance of keratinic fibers, in particular human hair;

Combability of keratinic fibers, in particular human hair; Delaying the aging process of keratinic fibers, especially human hair;

Restructurability of keratinic fibers, especially human hair, during and after the perming process;

Reducing the decrease in elasticity of keratinic fibers, in particular human hair, when damaged by atmospheric agents in which a hair treatment composition containing - in each case by weight - a) 0.0001 to 10 wt .-% of at least one oligopeptide containing at least one amino acid sequence Glu-Glu -Glu, wherein the amino group is free or protonated and the carboxy groups may be present freely or deprotonated,

b) 0.0001 to 10 wt .-% of at least one ester of hyaluronic acid with lipoic acid, formic acid or mixtures thereof

applied to the keratin fibers, left there for 5 seconds to 10 minutes and then rinsed out.

With respect to further preferred embodiments of the method according to the invention mutatis mutandis applies to the means of the invention.

Claims

claims:

1. hair treatment composition containing - in each case based on its weight - a) 0.0001 to 10 wt .-% of at least one oligopeptide, the at least one amino acid sequence Glu-Glu-Glu

Formic acid or mixtures thereof.

Hair treatment composition according to claim 1, characterized in that the oligopeptide 5 to 15 amino acids, preferably 6 to 13 amino acids, more preferably 7 to 12 amino acids and in particular 8, 9 or 10 amino acids and a molecular weight of 650 to 3000 Da, preferably from 750 to 2500 Da, more preferably from 850 to 2000 Da and in particular from 1000 to 1600 Da.

Hair treatment composition according to one of claims 1 or 2, characterized in that the oligopeptide Tyr-Glu-Glu-Glu-Ile

wherein the amino group may be free or protonated and the carboxy groups may be free or deprotonated.

4. hair treatment composition according to one of claims 1 to 3, characterized in that the ligopeptide at least one amino acid sequence Tyr-Glu-Glu-Glu-Ile-Arg-Val-Leu

wherein the amino groups are free or protonated and the carboxy groups may be free or deprotonated,

Hair treatment composition according to one of claims 1 to 4, characterized in that it is 0.0005 to 7.5 wt .-%, preferably 0.001 to 6 wt .-%, more preferably 0.005 to 5 wt .-%, more preferably 0.01 to 4 wt .-% and in particular 0.1 to 3 wt .-% of at least one ester of hyaluronic acid with lipoic acid, formic acid or mixtures thereof of the formula (I)

in the

X is selected from H, Na and K,

- n stands for numbers from 100 to 10000, and

R1, R2, R3 and R4 are independently selected from -H, -C (0) -H and

with the proviso that at least one of R1, R2, R3 and R4 is other than -H. Hair treatment composition according to one of claims 1 to 5, characterized in that it is 0.0005 to 7.5 wt .-%, preferably 0.001 to 6 wt .-%, more preferably 0.005 to 5 wt .-%, more preferably 0.01 to 4 wt .-% and in particular 0.1 to 3 wt .-% of at least one ester of hyaluronic acid with lipoic acid containing at least one recurring unit of Formula (II)

in the

X is selected from H, Na and K,

n stands for numbers from 1 to 10000, and

R1, R2 and R3 are independently selected from -H, -C (0) -H and

7. Hair treatment composition according to one of claims 1 to 6, characterized in that it 0.0005 to 7.5 wt .-%, preferably 0.001 to 6 wt .-%, more preferably 0.005 to 5 wt .-%, more preferably 0 , 01 to 4 wt .-% and in particular 0.1 to 3 wt .-% of at least one ester of hyaluronic acid with formic acid having at least one recurring unit of the formula (VI)

(VI)

in the

X is selected from H, Na and K,

- n stands for numbers from 100 to 10000, and

R1, R2 and R3 are independently selected from -H, -C (0) -H and

8. hair treatment composition according to one of claims 1 to 7, characterized in that it - based on its weight - 0.5 to 70 wt .-%, preferably 1 to 60 wt .-%, more preferably 2.5 to 35 wt. % and in particular from 5 to 25% by weight of anionic and / or nonionic and / or cationic and / or amphoteric surfactant (s).

9. hair treatment composition according to one of claims 1 to 8, characterized in that it - based on its weight - 0.05 to 7.5 wt .-%, preferably 0.1 to 5 wt .-%, particularly preferably 0.2 up to 3.5% by weight and in particular from 0.25 to 2.5% by weight of cationic polymer (s), preferred cationic polymer (s) being / are selected from

Poly (methacryloyloxyethyltrimethylammonium chloride) (INCI: Polyquaternium-37) and / or;

quaternized cellulose derivatives (INCI: Polyquaternium 10) and / or cationic alkyl polyglycosides and / or

cationised honey and / or

cationic guar derivatives and / or

polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid and / or

Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate and / or

Vinylpyrrolidone-Vinylimidazoliummethochlorid copolymers and / or quaternized polyvinyl alcohol and / or

Polyquaternium 2 and / or

Polyquaternium-7 and / or

Polyquaternium 17 and / or

Polyquaternium 18 and / or

Polyquaternium 24 and / or

Polyquaternium 27.

10. A method for improving at least one of the properties

Combability of keratinic fibers, in particular human hair; Delaying the aging process of keratinic fibers, in particular human hair;

Reduction in the elasticity of keratinic fibers, in particular human hair when damaged by atmospheric agents, characterized in that a hair treatment composition containing - in each case based on

Weight - c) from 0.0001 to 10% by weight of at least one oligopeptide containing at least one amino acid sequence Glu-Glu-Glu

wherein the amino group may be free or protonated and the carboxy groups may be free or deprotonated,

d) from 0.0001 to 10% by weight of at least one ester of hyaluronic acid with lipoic acid,

Formic acid or mixtures thereof